One-dimensional polymers based on [{CpMo(CO)2}2(mu,eta2-P2)]: solid-state conformation analysis by NMR spectroscopy...

Area of Science:

• Inorganic Chemistry
• Materials Science
• Organometallic Chemistry

Background:

• Diphosphene complexes are versatile building blocks in coordination chemistry.
• The synthesis of novel polymeric materials with interesting electronic and structural properties is an active area of research.

Purpose of the Study:

• To synthesize and characterize novel one-dimensional linear polymers using a diphosphene-molybdenum complex and copper(I) halides.
• To investigate the solid-state structures of the synthesized polymers.
• To understand the influence of structure on spectroscopic properties using phosphorus-31 magic angle spinning (MAS) NMR and density functional theory (DFT) calculations.

Main Methods:

• Reaction of [{CpMo(CO)2}2(mu,eta2-P2)] (1) with copper(I) halides (CuCl, CuBr, CuI) and copper(II) halides (CuCl2, CuBr2).
• Solid-state structure determination.
• Phosphorus-31 magic angle spinning (MAS) NMR spectroscopy.
• Density functional theory (DFT) calculations on model compounds.

Main Results:

• Quantitative formation of one-dimensional linear polymers [CuX{Cp2Mo2(CO)4(mu,eta2:eta1:eta1-P2)}](infinity) (X=Cl, Br, I).
• Structural comparison of the synthesized polymers.
• Correlation between solid-state structures and (31)P MAS NMR spectra.
• DFT calculations provided insights into the observed spectroscopic behavior.

Conclusions:

• The reaction provides a facile route to novel diphosphene-bridged copper-molybdenum coordination polymers.
• The structural diversity of these polymers significantly impacts their (31)P MAS NMR spectral features.
• DFT calculations are valuable tools for interpreting the structure-spectroscopy relationships in these complex materials.